Crosslinked tinted polymers

Abstract

The invention relates to a novel process for the production of tinted mouldings, in particular tinted contact lenses, in which a crosslinkable tinted polymer comprising units containing a crosslinkable group and units containing a reactive dye radical is crosslinked in solution, and to tinted mouldings, in particular tinted contact lenses, obtainable by this process. The present invention likewise relates to novel crosslinkable tinted polymers comprising units containing a crosslinkable group and units containing a reactive dye radical which can be employed in the novel process, in particular derivatives of a polyvinyl alcohol having a molecular weight of at least about 2000, to crosslinked tinted polymers, either homopolymers or copolymers, made from these novel crosslinkable tinted polymers containing a reactive dye radical, a process for the preparation of the novel crosslinkable tinted polymers comprising units containing a crosslinkable group and units containing a reactive dye radical and the homopolymers and copolymers obtainable therefrom, to tinted mouldings made from said homopolymers or copolymers, in particular tinted contact lenses made from these homopolymers or copolymers, and to a process for the production of tinted contact lenses using said homopolymers or copolymers.

Claims

1. A process for the production of crosslinked tinted mouldings, which comprises the following steps:

a) preparation of an essentially aqueous solution of a water-soluble crosslinkable tinted polymer comprising units containing a crosslinkable group and units containing a bonded reactive dye radical,

b) introduction of the resultant solution into a mould,

c) initiation of the crosslinking in water or in an organic solvent in which the crosslinkable tinted polymer is dissolved, and

d) opening of the mould so that the moulding can be removed.

2. A process according to claim 1, wherein the mouldings are contact lenses.

3. A process according to claim 1, wherein the water-soluble crosslinkable tinted polymer of step a) is derived from a starting polymer containing, on or in the polymer chain, a functional group which can react with a reactive dye.

4. A process according to claim 3, wherein the water-soluble crosslinkable tinted polymer of step a) is derived from polyvinyl alcohol.

5. A process according to claim 3, wherein the water-soluble crosslinkable tinted polymer of step a) comprises units in the polymer chain which are derived from the following monomer units: a vinyllactam, vinyl alcohol, if desired a vinyl (lower alkane)carboxylate, a vinylic crosslinking agent and, if desired, a vinylic photoinitiator.

6. A process according to claim 5, wherein the polymer is a terpolymer of vinylpyrrolidone, vinyl acetate and vinyl alcohol.

7. A process according to claim 1, wherein the essentially aqueous solution of the water-soluble crosslinkable tinted polymer is free or essentially free from undesired constituents, such as, in particular from monomeric, oligomeric or polymeric starting compounds used for the preparation of this polymer, or from by-products formed during the preparation of this polymer, or from impurities present in the reactive dyes.

8. A process according to claim 1, wherein the essentially aqueous solution of the water-soluble crosslinkable tinted polymer is used without addition of a comonomer, in particular a vinylic comonomer.

9. A process according to claim 1, wherein an initiator for the crosslinking is added to the solution of the water-soluble, crosslinkable tinted polymer.

10. A process according to claim 1, wherein the crosslinking is not followed by extraction in order to remove undesired constituents.

11. A process according to claim 1, wherein the reactive dye is covalently bonded to the polymer backbone either directly via an ether, thioether, amino or amido group or via a bivalent or trivalent bridge.

12. A process according to claim 11, wherein the bridge is a trivalent bridge derived from an.omega.-amino-C.sub.1 -C.sub.12 alkylaldehyde acetal.

13. A process according to claim 1, which comprises the following steps:

a) preparation of an essentially aqueous solution of a water-soluble crosslinkable tinted polymer comprising units containing a crosslinkable group and units containing a reactive dye radical covalently bonded to the polymer backbone either directly or via a bridge, which solution is free or essentially free from undesired constituents, such as, in particular, from monomeric, oligomeric or polymeric starting compounds used for the preparation of this polymer or from by-products formed during the preparation of this polymer, or from impurities present in the reactive dyes, and is used without addition of a comonomer,

b) introduction of the resultant solution into a mould,

c) initiation of the crosslinking, and

d) opening of the mould so that the moulding can be removed.

14. A process according to claim 13, wherein the mouldings are tinted contact lenses.

15. A process according to claim 14 for the production of a contact lens, wherein the essentially aqueous solution is a purely aqueous solution or a solution in an artificial, preferably buffered, tear fluid.

16. A process according to claim 14 for the production of a tinted contact lens, wherein a crosslinking initiator is added to the solution, and the crosslinking takes place by photocrosslinking.

17. A tinted moulding, in particular a tinted contact lens, obtainable by a process according to claim 1.

18. A tinted contact lens according to claim 17, which is suitable for its intended use without extraction.

19. A tinted contact lens obtainable according to claim 14, which is suitable for its intended use without extraction.

20. A crosslinkable tinted polymer comprising units containing a crosslinkable group of the formula I ##STR33## in which R is alkylene having up to 12 carbon atoms, R.sub.1 is hydrogen or lower alkyl, and R.sub.2 is an olefinically unsaturated, electron-withdrawing, copolymerizable radical, having up to 25 carbon atoms, and R.sub.3 is hydrogen, a C.sub.1 -C.sub.6 alkyl group or a cycloalkyl group, and comprising units containing a covalently bonded reactive dye, where the covalent bond to the polymer backbone is, either direct via an ether, thioether, amino, imino or amido group or via a bivalent or trivalent bridge.

21. A crosslinkable tinted polymer according to claim 20, in which the units containing a ##STR34## in which: RF' is a radical of the formula ##STR35## D is a radical of an organic dye, R.sub.14 is a divalent electron-withdrawing group,

U is hydrogen or halogen,

R is a divalent radical of a C.sub.1 -C.sub.12 alkane,

R.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.3 is hydrogen, C.sub.1 -C.sub.6 alkyl or cycloalkyl, and

Y is --O-- or -N(R.sub.1)--.

22. A crosslinkable tinted polymer according to claim 21, wherein R.sub.1 and R.sub.3 are hydrogen, R is C.sub.1 -C.sub.4 alkylene, and RF' and Y are as defined above.

23. A crosslinkable tinted polymer according to claim 20, wherein the covalently bonded reactive dye is derived from a reactive dye which conforms to the general formula XVII or XIII ##STR36## in which D is a radical of an organic dye, R.sub.14 is a divalent, organic, electron-withdrawing group,

U is hydrogen or halogen, and

V is a leaving group, or mixtures thereof.

24. A crosslinkable tinted polymer according to claim 23, wherein D is the radical of an azo (monoazo or disazo), phthalocyanine, azomethine, nitro, metal complex or anthraquinone dye.

25. A crosslinkable tinted polymer according to claim 23, wherein R.sub.14 is --CO--, --SO.sub.2 --, --SO--, --NHCO-- or --NHSO.sub.2 --.

26. A crosslinkable tinted polymer according to claim 21, wherein the reactive dye radical

RF' is derived from

Remazol Schwarz B (Reactive Black 5),

Remazol Brillantblau R (Reactive Blue 19, Duasyn-Blau R-R),

Remazol Tuirkisblau G (Reactive Blue 21, Duasyn-Blau R-KG),

Remazol Goldorange 3G (Reactive Orange 78),

Remazol Brillantrot F3B (Reactive Red 180, Duasyn-Rot R-F3B),

Remazol Gelb GR (Reactive Yellow 15),

Remazol Brillantgelb GL (Reactive Yellow 37, Duasyn-Gelb R-GL),

Duasyn-Gelb R-R (mixture of Reactive Yellow 17 and Reactive Yellow 15),

Remazol Brillantgrun 6B (Reactive Blue 38, Duasyn-Grun R-K6B),

Remazol Schwarz RL (Reactive Black 31, Duasyn-Schwarz R-KRL),

Duasyn-Schwarz R-N (mixture of Reactive Black 5 and Reactive Orange 72),

Remazol Brillantorange 3R (Reactive Orange 16),

Remazol Brillantblau B,

Remazol Brillantblau BB,

Remazol Druckschwarz G,

Remazol Rot B, or Duasyn-Blau R-UG.

27. A crosslinkable tinted polymer according to claim 20, which is a derivative of a polyvinyl alcohol having a mean molecular weight of at least about 2000 which comprises from about 0.5 to about 80%, based on the number of hydroxyl groups in the polyvinyl alcohol, of crosslinkable units of the formula I ##STR37## in which R is alkylene having up to 12 carbon atoms, R.sub.1 is hydrogen or lower alkyl, and R.sub.2 is an olefinically unsaturated, electron-withdrawing, copolymerizable radical, having up to 25 carbon atoms, and R.sub.3 is hydrogen, a C.sub.1 -C.sub.6 alkyl group or a cycloalkyl group.

28. A crosslinkable tinted polymer according to claim 27, in which R.sub.2 is an olefinically unsaturated acyl radical of the formula R.sub.30 --CO--, in which R.sub.30 is an olefinically unsaturated, copolymerizable radical having 2 to 24 carbon atoms.

29. A crosslinkable tinted polymer according to claim 28, in which R.sub.30 is alkenyl having 2 to 8 carbon atoms.

30. A crosslinkable tinted polymer according to claim 27, in which the radical R.sub.2 is a radical of the formula II

31. A crosslinkable tinted polymer according to claim 27, which is a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000 which comprises from about 0.5 to about 80%, based on the number of hydroxyl groups in the polyvinyl alcohol, of units of the formula III ##STR38## in which R is lower alkylene, R.sub.1 is hydrogen or lower alkyl, p has the value zero or one, q has the value zero or one, R.sub.30 is an olefinically unsaturated, copolymerizable radical having 2 to 8 carbon atoms, and R.sub.4 and R.sub.5, independently of one another, are lower alkylene having 2 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, a saturated bivalent cycloaliphatic group having 6 to 10 carbon atoms, arylenealkylene or alkylenearylene having 7 to 14 carbon atoms or arylenealkylenearylene having 13 to 16 carbon atoms.

32. A crosslinkable tinted polymer according to claim 31, in which R is lower alkylene having up to 6 carbon atoms, p is zero and R.sub.30 is alkenyl having 2 to 8 carbon atoms.

33. A crosslinkable tinted polymer according to claim 31, in which R is lower alkylene having up to 6 carbon atoms, p is one, q is zero, R.sub.5 is lower alkylene having 2 to 6 carbon atoms, and R.sub.30 is alkenyl having 2 to 8 carbon atoms.

34. A crosslinkable tinted polymer according to claim 31, in which R is lower alkylene having up to 6 carbon atoms, p is one, q is one, R.sub.4 is lower alkylene having 2 to 6 carbon atoms, phenylene, unsubstituted or substituted by lower alkyl, cyclohexylene or cyclohexylene(lower alkylene), unsubstituted or substituted by lower alkyl, phenylene(lower alkylene), (lower alkylene)phenylene or phenylene(lower alkylene)phenylene, R.sub.5 is lower alkylene having 2 to 6 carbon atoms, and R.sub.30 is alkenyl having 2 to 8 carbon atoms.

35. A crosslinkable tinted polymer according to claim 27, which is a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000 which comprises from about 1 to about 15%, based on the number of hydroxyl groups in the polyvinyl alcohol, of units of the formula I.

36. A compound of the formula XI ##STR39## in which the symbols R' and R" are hydrogen or lower alkyl or lower alkanoyl, and the other symbols R.sub.3, R, R.sub.1 and RF' are as defined in claim 21.

37. A crosslinked tinted polymer obtainable by photocrosslinking a crosslinkable tinted polymer according to claim 20 in the presence or absence of an additional vinylic comonomer.

38. A crosslinked tinted polymer according to claim 37, wherein said crosslinked tinted polymer is photocrosslinked in essentially pure form additional vinylic comonomerl.

39. A crosslinked tinted polymer according to claim 38, where the crosslinkable tinted polymer is converted into essentially pure form by single or repeated ultrafiltration.

40. A crosslinked tinted polymer according to claim 37, wherein said crosslinked tinted polymer is photocrosslinked in the absence of an additional vinylic comonomer.

41. A crosslinked tinted polymer according to claim 37, wherein said crosslinked tinted polymer is photocrosslinked in the presence of from 0.5 to 80 units of an additional vinylic comonomer per unit of the formula I.

42. A process for the preparation of a crosslinked tinted polymer according to claim 37, which comprises photocrosslinking said crosslinkable tinted polymer ccording to claim 20 in the presence or absence of an additional vinylic comonomer.

43. A process according to claim 42, wherein the crosslinkable tinted polymer is employed in essentially pure form.

44. A process according to claim 43, wherein the crosslinkable tinted polymer is converted into essentially pure form by single or repeated ultrafiltration.

45. A process according to claim 42, which is carried out in a solution.

46. A tinted moulding essentially comprising a crosslinked tinted polymer according to claim 37.

47. A tinted moulding according to claim 46, which is a tinted contact lens.

48. A process for the production of a tinted moulding according to claim 46, which comprises photocrosslinking said crosslinkable tinted polymer in a closed mould in the presence or absence of an additional vinylic comonomer.

49. A process for the production of a tinted contact lens according to claim 47, which comprises photocrosslinking said crosslinkable tinted polymer in a closed contact-lens mould by the full-mould process in the presence or absence of an additional vinylic comonomer.